In the recent drive for higher integration and operating speeds in LSI devices, the pattern rule is made drastically finer. The photolithography which is currently on widespread use in the art is approaching the essential limit of resolution determined by the wavelength of a light source.
As the light source used in the lithography for resist pattern formation, g-line (436 nm) or i-line (365 nm) from a mercury lamp was widely used. One means believed effective for further reducing the feature size is to reduce the wavelength of exposure light. For the mass production process of 64 MB dynamic random access memories (DRAM, feature size 0.25 μm or less) and later ones, the exposure light source of i-line (365 nm) was replaced by a KrF excimer laser having a shorter wavelength of 248 nm.
However, for the fabrication of DRAM with a degree of integration of 256 MB and 1 GB or more requiring a finer patterning technology (feature size 0.2 μm or less), a shorter wavelength light source is required. Over a decade, photolithography using ArF excimer laser light (193 nm) has been under active investigation.
It was expected at the initial that the ArF lithography would be applied to the fabrication of 180-nm node devices. However, the KrF excimer lithography survived to the mass-scale fabrication of 130-nm node devices. So, the full application of ArF lithography started from the 90-nm node. The ArF lithography combined with a lens having an increased numerical aperture (NA) of 0.9 is considered to comply with 65-nm node devices.
For the next 45-nm node devices which required an advancement to reduce the wavelength of exposure light, the F2 lithography of 157 nm wavelength became a candidate. However, for the reasons that the projection lens uses a large amount of expensive CaF2 single crystal, the scanner thus becomes expensive, hard pellicles are introduced due to the extremely low durability of soft pellicles, the optical system must be accordingly altered, and the etch resistance of resist is low; the postponement of F2 lithography and the early introduction of ArF immersion lithography were advocated (see Proc. SPIE Vol. 4690 xxix).
In the ArF immersion lithography, the space between the projection lens and the wafer is filled with water. Since water has a refractive index of 1.44 at 193 nm, pattern formation is possible even using a lens with NA of 1.0 or greater. Theoretically, it is possible to increase the NA to 1.35. The resolution is improved by an increment of NA. A combination of a lens having NA of at least 1.2 with ultra-high resolution technology suggests a way to the 45-nm node (see Proc. SPIE Vol. 5040, p 724).
With respect to the immersion lithography, several problems associated with the presence of water on resist were pointed out. Because the photoacid generator in the resist film, the acid generated therefrom upon exposure, and the amine compound added to the resist as a quencher can be leached in water in contact with the resist film, pattern profile changes occur. The pattern collapses due to swelling of the resist film with water.
With respect to the leaching of resist components into water, a study started from the standpoint of preventing the projection lens of the lithography system from contamination. Several lithography system manufacturers proposed the limit of leach-outs.
For overcoming these problems, it was proposed to provide a protective coating of perfluoroalkyl compound between the resist film and water (see the 2nd Immersion Workshop, Jul. 11, 2003, Resist and Cover Material Investigation for Immersion Lithography). The provision of such a protective coating avoids direct contact between the resist film and water and inhibits the resist film from being leached with water.
However, protective coatings made of perfluoroalkyl compounds use fluorocarbons like Freon® as the diluent for controlling a coating thickness. As is well known, the use of fluorocarbons is a consideration in view of environmental protection. In addition, the protective coating must be stripped using fluorocarbon, prior to development of the resist film. Therefore, special units for coating and stripping of the protective film must be added to the existing system. Fluorocarbon solvents add to the expense. These factors raise serious problems on practical use.
One means proposed for mitigating practical drawbacks of the protective film of solvent stripping type is a protective film of the type which is soluble in alkaline developer (JP-A 2005-264131). The alkali-soluble protective film is epoch-making in that it eliminates a need for a stripping step or a special stripping unit because it can be stripped off at the same time as the development of a photoresist film. However, on use of a protective film of alkaline developer soluble type, the step of coating a protective film is still necessary. Also, the diluent solvent necessary to form a coating solution of protective film material must be selected from those solvents in which the photoresist film is not readily dissolved, because the solvent should not attack the underlying film or photoresist film. To avoid troubles like resin precipitation resulting from mixing of the resist and protective film coating solutions, a special unit for coating of a protective film is needed.
As discussed above, the immersion lithography suffers from drawbacks including an increased cost due to use of a protective film. One effort taken to overcome these problems is the development of a resist composition for the immersion lithography which is endowed with a barrier property against water and thus eliminates a need for protective film. This will achieve a cost reduction as well.
The ArF immersion lithography systems commercially available at the present are designed such that water is partly held between the projection lens and the wafer rather than immersing the resist-coated substrate fully in water, and exposure is carried out by scanning the wafer-holding stage at a speed of 300 to 550 mm/sec. Because of such high-speed scanning, water cannot be held between the projection lens and the wafer, and water droplets are left on the surface of the resist film or protective film after scanning. It is believed that residual droplets cause defective pattern formation.
To eliminate the droplets remaining on the surface of the photoresist or protective film after scanning, it is necessary to improve the flow or mobility of water on the relevant coating film. It is reported that the number of defects associated with the immersion lithography can be reduced by increasing the receding contact angle of the photoresist or protective film with water. See 2nd International Symposium on Immersion Lithography, 12-15 Sep., 2005, Defectivity data taken with a full-field immersion exposure tool, Nakano et al.
Efforts were made to add a polymeric surfactant having hexafluoroalcohol groups to a photoresist material in order to increase the water repellency of resist surface as spin coated. JP-A 2006-48029, JP-A 2006-309245, and JP-A 2007-187887 disclose hexafluoroalcohol-containing surfactants based on methacrylic polymers.
On the other hand, in the course of 157-nm resist material development, a study was made on a copolymer of a-trifluoromethyl acrylate and norbornene (Proc. SPIE, Vol. 4690, p 18, 2002). It is a copolymer of α-trifluoromethyl acrylate and norbornene in a ratio of 2:1 and specifically an alternating copolymer characterized by a regular arrangement of molecules.
It is reported in Progress in Organic Coatings, 31, p 97-104 (1997) that a fluoroalkyl group with a negative electric charge coordinates with a hydrogen atom of water whereas an alkyl group coordinates with an oxygen atom of water. It is described that an alkyl-bearing compound is superior in water sliding to a fluoroalkyl-bearing compound because the alkyl group has a longer coordination distance with water. The alkyl group, when bonded to a silicon atom, has a further extended coordination distance with water. Then the co-presence of dimethylsiloxy and fluoroalkyl groups contributes to an improvement in water sliding. This technology is commercially implemented as coatings on window glass of automobiles. JP-A 2007-140446 describes a protective coating for immersion lithography in which an alternate coordination of fluoroalkyl and alkyl groups disturbs the orientation of water to elongate the orientation distance with water, achieving an outstanding improvement in water sliding. Of these protective coatings, the copolymer of a-trifluoromethyl acrylate and norbornene exhibits the best water sliding performance.
In the immersion lithography, it is required to improve throughputs. For improved productivity, the exposure time must be reduced, which in turn requires high-speed scanning operation of the stage. In order to follow the high-speed traveling stage while holding water beneath the lens, it is desired to have a resist material having higher water sliding performance.
To facilitate high-speed scanning, a resist film on a wafer must have a large receding contact angle. It is noted that when a droplet of water is on a resist film on a wafer and the wafer is gradually inclined, the inclination angle at which the droplet starts sliding down is defined as the “sliding angle” and at this instant, the droplet has an “advancing contact angle” and a “receding contact angle.” Specifically, the resist film is required to have a receding contact angle of at least 70 degrees, and preferably at least 80 degrees, when a 50 μL droplet of water is applied. On the other hand, in the case of an exposure tool equipped with a nozzle mechanism of providing an air curtain for holding water, bubbles can be entrained from the front in the scanning direction whereby bubble defects may be introduced. To prevent bubble entrainment, an advancing contact angle of up to 95 degrees is required. Thus excellent water sliding performance meeting a receding contact angle of at least 70 degrees, especially at least 80 degrees, and an advancing contact angle of up to 95 degrees is required.
Resist compositions for mask blanks suffer from problems including a change of sensitivity during long-term exposure in vacuum and long-term stability after coating. With respect to the stability in vacuum, an improvement is made by a combination of acid labile groups of acetal and tertiary ester types (U.S. Pat. No. 6,869,744). It is believed that after coating of a resist composition, an amine component is adsorbed to the resist film surface whereby the resist varies its sensitivity or profile. A method of preventing adsorption of an amine component or a method of modifying the surface of a resist film is believed effective for improving the stability after coating.
It is reported that the profile of a line-and-space pattern differs between a bright pattern where a peripheral portion around the pattern is exposed and a dark pattern where a peripheral portion around the pattern is not exposed. When a peripheral portion around the pattern is exposed, the acid generated in the peripheral portion can evaporate during PEB to cover the pattern area, whereby the line pattern undergoes a film slimming. When a peripheral portion around the pattern is not exposed, no acid is supplied from the peripheral portion and inversely, amine evaporates whereby the line pattern takes a bulged top profile. This difference of profile, which is referred to as “dark-bright difference,” occurs in the immersion lithography, but a similar phenomenon also occurs in dry lithography and electron beam vacuum lithography. The dark-bright difference can be reduced by providing a protective coating on the resist film.